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1.
J Radiat Res ; 64(2): 399-411, 2023 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-36763853

RESUMO

Human head and neck squamous cell carcinoma cells transfected with mutant TP53 (SAS/mp53) or neo vector (SAS/neo) were inoculated subcutaneously into left hind legs of nude mice. After the subcutaneous administration of a 10B-carrier, boronophenylalanine-10B (BPA) or sodium mercaptododecaborate-10B (BSH), at two separate concentrations, the 10B concentrations in tumors were measured using γ-ray spectrometry. The tumor-bearing mice received 5-bromo-2'-deoxyuridine (BrdU) continuously to label all intratumor proliferating (P) tumor cells, then were administered with BPA or BSH. Subsequently, the tumors were irradiated with reactor neutron beams during the time of which 10B concentrations were kept at levels similar to each other. Following irradiation, cells from some tumors were isolated and incubated with a cytokinesis blocker. The responses of BrdU-unlabeled quiescent (Q) and total (= P + Q) tumor cells were assessed based on the frequencies of micronucleation using immunofluorescence staining for BrdU. In both SAS/neo and SAS/mp53 tumors, the compound biological effectiveness (CBE) values were higher in Q cells and in the use of BPA than total cells and BSH, respectively. The higher the administered concentrations were, the smaller the CBE values became, with a clearer tendency in SAS/neo tumors and the use of BPA than in SAS/mp53 tumors and BSH, respectively. The values for BPA that delivers into solid tumors more dependently on uptake capacity of tumor cells than BSH became more alterable. Tumor micro-environmental heterogeneity might partially influence on the CBE value. The CBE value can be regarded as one of the indices showing the level of intratumor heterogeneity.


Assuntos
Terapia por Captura de Nêutron de Boro , Carcinoma de Células Escamosas , Neoplasias de Cabeça e Pescoço , Animais , Camundongos , Humanos , Bromodesoxiuridina/análise , Carcinoma de Células Escamosas/radioterapia , Carcinoma de Células Escamosas/patologia , Terapia por Captura de Nêutron de Boro/métodos , Camundongos Nus , Compostos de Boro/uso terapêutico , Boroidretos/química , Compostos de Sulfidrila , Proteína Supressora de Tumor p53
2.
Molecules ; 27(6)2022 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-35335336

RESUMO

In hydrolysis and electro-oxidation of the borohydride anion BH4-, key reactions in the field of energy, one critical short-living intermediate is BH3OH-. When water was used as both solvent and reactant, only BH3OH- is detected by 11B NMR. By moving away from such conditions and using DMF as solvent and water as reactant in excess, four 11B NMR quartets were observed. These signals were due to BH3-based intermediates as suggested by theoretical calculations; they were DMF·BH3, BH3OH-, and B2H7- (i.e., [H3B-H-BH3]- or [H4B-BH3]-). Our results shed light on the importance of BH3 stemming from BH4- and on its capacity as Lewis acid to interact with Lewis bases such as DMF, OH-, and BH4-. These findings are important for a better understanding at the molecular level of hydrolysis of BH4- and production of impurities in boranes synthesis.


Assuntos
Boranos , Ânions , Boroidretos/química , Hidrólise , Água
3.
Cells ; 10(11)2021 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-34831105

RESUMO

Boron neutron capture therapy (BNCT) is a cancer-selective radiotherapy that utilizes the cancer targeting 10B-compound. Cancer cells that take up the compound are substantially damaged by the high liner energy transfer (LET) particles emitted mainly from the 10B(n, α7Li reaction. BNCT can minimize the dose to normal tissues, but it must be performed within the tolerable range of normal tissues. Therefore, it is important to evaluate the response of normal tissues to BNCT. Since BNCT yields a mixture of high and low LET radiations that make it difficult to understand the radiobiological basis of BNCT, it is important to evaluate the relative biological effectiveness (RBE) and compound biological effectiveness (CBE) factors for assessing the responses of normal tissues to BNCT. BSH and BPA are the only 10B-compounds that can be used for clinical BNCT. Their biological behavior and cancer targeting mechanisms are different; therefore, they affect the CBE values differently. In this review, we present the RBE and CBE values of BPA or BSH for normal tissue damage by BNCT irradiation. The skin, brain (spinal cord), mucosa, lung, and liver are included as normal tissues. The CBE values of BPA and BSH for tumor control are also discussed.


Assuntos
Boroidretos/química , Terapia por Captura de Nêutron de Boro , Fenilalanina/química , Compostos de Sulfidrila/química , Animais , Humanos , Neoplasias/patologia , Neoplasias/radioterapia , Eficiência Biológica Relativa , Distribuição Tecidual
4.
Eur Rev Med Pharmacol Sci ; 25(17): 5507-5510, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-34533797

RESUMO

OBJECTIVE: The paper presents the antibacterial activity of silver nanoparticles (AgNPs) when conjugated with Levofloxacin. The AgNPs used in this study were synthesized from silver nitrate using sodium borohydride as a reducing agent. MATERIALS AND METHODS: Levofloxacin activity was determined by minimum inhibitory concentrations (MICs) and also the erythrocyte hemolytic assay determined the capability of conjugation to cause hemolysis in human erythrocyte. RESULTS: The synthesis of levofloxacin-AgNP conjugates was confirmed by ultraviolet/visible (UV/vis) spectroscopy. A peak absorption value between 400-450 nm for the extract and the color change to dark brown were corresponding to the plasmon absorbance of AgNPs. On the other hand, levofloxacin-AgNPs could be effective against methicillin-resistant Staphylococcus aureus (MRSA). The MICs of levofloxacin and levofloxacin-AgNPs were 12 and 10 µM, respectively. CONCLUSIONS: These findings indicated that levofloxacin-AgNPs had an effective bactericidal activity against the bacterial MRSAs. This conjugation appeared to inhibit bacterial adaptive capabilities, which leads to inhibition of bacterial resistance.


Assuntos
Antibacterianos/farmacologia , Levofloxacino/farmacologia , Nanopartículas Metálicas , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacos , Antibacterianos/administração & dosagem , Antibacterianos/toxicidade , Boroidretos/química , Hemólise/efeitos dos fármacos , Humanos , Levofloxacino/administração & dosagem , Levofloxacino/toxicidade , Testes de Sensibilidade Microbiana , Nitrato de Prata/química
5.
ACS Appl Mater Interfaces ; 13(33): 39806-39818, 2021 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-34387459

RESUMO

Silver nanomaterials have attracted a great deal of interest due to their broad-spectrum antimicrobial activity. However, it is still challenging to balance the high antibacterial efficiency with low damage to biological cells of silver nanostructures, especially when the diameter decreases to less than 10 nm. Here, we developed a new type of Ag nanohybrid material via a unimolecular micelle template method, which presents amazing antibacterial activities and almost noncytotoxicity. First, water-soluble multiarm star-shaped brushlike copolymer α-CD-g-[(PEO40-g-PAA50)-b-PEO5]18 was precisely synthesized and its micelle behavior in different solvents was revealed. Then, nanocrystal clusters assembled by Ag grains (Ag@Template NCs) were prepared through an in situ redox route using the unimolecular micelle of α-CD-g-[(PEO40-g-PAA50)-b-PEO5]18 as the soft template, AgNO3 as a precursor, and tetrabutylammonium borohydride (TBAB) as the reducing agent. The overall size of the achieved Ag@Template NCs is controlled by the template structure at around 40 nm (Dh in DMF), and the size of the Ag grain can be easily regulated from ∼1 to ∼5 nm by adjusting the feeding ratio of AgNO3/acrylic acid (AA) units in the template from 1:10 to 1:1. Benefitting from the structural design of the template, all Ag@Template NCs prepared here exhibit excellent dispersibility and chemical stability in different aqueous environments (neutral, pH = 5.5, and 0.9% NaCl physiological saline solution), which play a crucial role in the long-term storage and potential application in a complex physiological environment. The antibacterial and cytotoxicity tests indicate that Ag@Template NCs display much better performance than Ag nanoparticles (Ag NPs), which have a comparable overall size of ∼25 nm. The inhibitory capability of Ag@Template NCs to bacteria strongly depends on the grain size. Specifically, the Ag@Template-1 NC assembled by the smallest grains (1.6 ± 0.3 nm) presents the best antibacterial activity. For E. coli (-), the MIC value is as low as 5 µg/mL (0.36 µg/mL of Ag), while for S. aureus (+), the value is around 10 µg/mL (0.72 µg/mL of Ag). The survival rate of L02 cells and lactate dehydrogenase assay together illustrate the low cytotoxicity possessed by the prepared Ag@Template NCs. Therefore, the proposed Ag@Template NC structure successfully resolves the high reactivity, instability, and fast oxidation issues of the ultrasmall Ag nanoparticles, and integrates high antibacterial efficiency and nontoxicity to biological cells into one platform, which implies its broad potential application in biomedicine.


Assuntos
Antibacterianos/efeitos adversos , Antibacterianos/química , Nanopartículas Metálicas/química , Prata/química , Antibacterianos/metabolismo , Boroidretos/química , Sobrevivência Celular/efeitos dos fármacos , Escherichia coli/efeitos dos fármacos , Humanos , Testes de Sensibilidade Microbiana , Tamanho da Partícula , Polímeros/química , Compostos de Amônio Quaternário/química , Staphylococcus aureus/efeitos dos fármacos , Propriedades de Superfície , Nanomedicina Teranóstica
6.
Bioorg Med Chem Lett ; 48: 128245, 2021 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-34242759

RESUMO

Nitroaromatic antibiotics are used to treat a variety of bacterial and parasitic infections. These prodrugs require reductive bioactivation for activity, which provides a pathway for the release of nitrogen oxide species such as nitric oxide, nitrite, and/or nitroxyl. Using sodium borohydride and 2-aminoethanol as model reductants, this work examines release of nitrogen oxide species from various nitroaromatic compounds through several characterization methods. Specifically, 4- and 5-nitroimidazoles reproducibly generate higher amounts of nitrite (not nitric oxide or nitroxyl) than 2-nitroimidazoles during the reaction of model hydride donors or thiols. Mass spectrometric analysis shows clean formation of products resulting from nucleophile addition and nitro group loss. 2-Nitrofurans generate nitrite upon addition of sodium borohydride or 2-aminoethanethiol, but these complex reactions do not produce clean organic products. A mechanism that includes nucleophile addition to the carbon ßto the nitro group to generate a nitronate anion followed by protonation and nitrous acid elimination explains the observed products and labeling studies. These systematic studies give a better understanding of the release mechanisms of nitrogen oxide species from these compounds allowing for the design of more efficient therapeutics.


Assuntos
Antibacterianos/química , Boroidretos/química , Nitritos/química , Nitrocompostos/química , Compostos de Sulfidrila/química , Estrutura Molecular
7.
Int J Biol Macromol ; 187: 386-398, 2021 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-34284055

RESUMO

In this study, tin oxide­cobalt oxide nanocatalyst was prepared by a simple method, which grew in spherical particles with an average diameter of 30 nm. Tin oxide-cobalt oxide was further wrapped in alginate polymer hydrogel (Alg@tin oxide-cobalt oxide), and both materials were utilized as nanocatalysts for the catalytic transformation of different pollutants. Tin oxide-cobalt oxide and Alg@tin oxide-cobalt oxide nanocatalysts were tested for the catalytic reduction of 4-nitrophenol, congo red, methyl orange, methylene blue (MB) and potassium ferricyanide in which sodium borohydride was used as a reducing agent. Tin oxide-cobalt oxide and Alg@tin oxide-cobalt oxide nanocatalysts synergistically reduced MB in shorter time (2.0 and 4.0 min) compared to other dyes. The reduction conditions were optimized by changing different parameters. The rate constants for MB reduction were calculated and found to be 1.5714 min-1 and 0.6033 min-1 using tin oxide-cobalt oxide and Alg@tin oxide-cobalt oxide nanocatalysts, respectively. Implementing Alg@tin oxide-cobalt oxide nanocatalyst toward MB reduction in real samples proved its efficacy in sea and well water samples. The catalyst could be easily recovered, recycled and revealed a minimal loss of nanoparticles, which offering a competition and replacement with reputable commercial catalysts.


Assuntos
Alginatos/química , Cobalto/química , Nanocompostos , Óxidos/química , Compostos de Estanho/química , Águas Residuárias/química , Poluentes Químicos da Água/química , Purificação da Água , Compostos Azo/química , Boroidretos/química , Catálise , Vermelho Congo/química , Ferricianetos/química , Cinética , Azul de Metileno/química , Nanotecnologia , Nitrofenóis/química , Oxirredução
8.
Int J Biol Macromol ; 182: 2003-2018, 2021 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-34029584

RESUMO

The presence of saccharin (SH) could be efficiently sensed (in the concentration range of 5 × 10-5 M to 5 × 10-1 M) through the interference synthesis of gum ghatti (GG) capped silver nanoparticles (GGAgNps). The synthesis used sodium borohydride and gum ghatti (GG) as the reducing and capping agents respectively. The strong hydrogen-bonding recognition between GG and SH was responsible for the interference. The intensity of the SPR peak of GGAgNps was found linearly dependent on [SH]. The SH detection was further enhanced when combo capping comprising of GG and chitosan (Ch) (in 1:1 weight ratio) was used while the use of gum acacia (GA) in place of Ch (in combo) decreased the detection sensitivity. The combo polysaccharide solutions had non-Newtonian behaviour and shear thinning property like GG. The method was also applied for the successful detection of SH in commercially available real juice samples.


Assuntos
Nanopartículas Metálicas/química , Gomas Vegetais/química , Sacarina/análise , Prata/química , Boroidretos/química , Concentração de Íons de Hidrogênio , Nanopartículas Metálicas/ultraestrutura , Tamanho da Partícula , Polissacarídeos/química , Nitrato de Prata/química , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de Fourier , Eletricidade Estática , Edulcorantes/análise , Fatores de Tempo , Viscosidade
9.
J Fluoresc ; 31(1): 73-83, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33078252

RESUMO

Boron neutron capture therapy (BNCT), a binary cancer therapeutic modality, has moved to a new phase since development of accelerator-based neutron sources and establishment of BNCT centers in Finland and Japan. That stimulated efforts for better boron delivery agent development. As liposomes have shown effective boron delivery properties and sufficient tumor retention, fluorescent liposome labelling may serve as a rapid method to study initial ability of newly synthesized liposomes to be captured by tumor cells prior to experiments on boron accumulation and neutron irradiation. In this work, we studied the accumulation and biodistribution of pegylated liposomes with encapsulated borocaptate (BSH) and a fluorescent label (Nile Red) in U87 (human glioblastoma), SW-620 (human colon carcinoma), SK-MEL-28 (human melanoma), FetMSC (mesenchymal human embryo stem cells), and EMBR (primary embryocytes) cell lines as well as an orthotopic xenograft model of U87 glioma in SCID mice. Results indicate that fluorescent microscopy is effective at determining the intracellular localization of the liposomes using a fluorescent label. The synthesized, pegylated liposomes showed higher accumulation in tumors compared to normal cells, with characteristic concentration peaks in SW-620 and U87 cell lines, and provided in vivo tumor selectivity with several-fold higher tumor tissue fluorescence at the 6-h timepoint. Graphical abstract Fluorescent images of U-87 glioma cells after 24 hours of incubation with BSH-containing liposomes labeled with lipophilic Nile Red (red color)and water-soluble FITC-Dextran (green color); cell nuclei in blue color (DAPI-staining) (×400). Scale bar is 50 µm. Fluorescent labelling serves as anexpress method to study liposome delivery efficiency prior to boron accumulation evaluation and BNCT irradiation experiments.


Assuntos
Boroidretos/química , Corantes Fluorescentes/química , Lipossomos/química , Boroidretos/uso terapêutico , Linhagem Celular Tumoral , Glioma/patologia , Humanos
10.
Int J Biol Macromol ; 166: 1258-1271, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33157136

RESUMO

Chitosan (Ch) capped Ch-CeO2, Ch-CeO2/Ag, Ch-CeO2/Pd and Ch-CeO2/Ag/Pd nanomaterials were fabricated using seedless and metal displacement plating method. The Ce4+ ions first formed complex with Ch through amino and hydroxyl groups and then reduced in presence of NaOH and molecular oxygen at higher temperature. Ch-Ag+ and Ch-Pd2+ complexes adsorbed on the surface of Ch-CeO2 and reduced under potential deposition. Ninhydrin reaction test was conducted to confirm the presence of chitosan on the surface of NMs. The catalytic efficiency was increases markedly with incorporating noble metal into Ch-CeO2 NMs. Ch-CeO2/Ag/Pd exhibits higher catalytic performance towards hydrogen generation due to the narrow band gap (2.65 eV) and smaller work function of CeO2 (ϕ = 2.8 eV) than that of Ag0(ϕ =4.6 eV) and Pd0 (ϕ = 5.2 eV). Hydrogen generation rates increases with temperature and activation energies were found to be 63.2, 60.3, 56.2 and 53.0 kJ/mol for Ch-CeO2, Ch-CeO2/Ag, Ch-CeO2/Pd, and Ch-CeO2/Ag/Pd, respectively. CeO2/Ag/Pd shows better catalytic efficiency due to the strong interaction between Ag/Pd metal and active support CeO2. The photocatalytic rates drastically inhibited with scavengers, demonstrate that the reactive radical oxygen species (HO and O2-), holes (h+) and electrons (e-) played major role in the NaBH4 hydrolysis.


Assuntos
Cério/química , Quitosana/química , Nanoestruturas/química , Adsorção , Boroidretos/química , Catálise , Entropia , Hidrogênio/química , Hidrólise , Nanoestruturas/ultraestrutura , Hidróxido de Sódio/química , Espectrometria por Raios X , Espectrofotometria Ultravioleta , Luz Solar , Temperatura , Viscosidade
11.
Anal Biochem ; 613: 114022, 2021 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-33217405

RESUMO

In a recent paper, we showed the difference between the first stage of the one-substrate and the two-substrate transketolase reactions - the possibility of transfer of glycolaldehyde formed as a result of cleavage of the donor substrate from the thiazole ring of thiamine diphosphate to its aminopyrimidine ring through the tricycle formation stage, which is necessary for binding and splitting the second molecule of donor substrate [O.N. Solovjeva et al., The mechanism of a one-substrate transketolase reaction, Biosci. Rep. 40 (8) (2020) BSR20180246]. Here we show that under the action of the reducing agent a tricycle accumulates in a significant amount. Therefore, a significant decrease in the reaction rate of the one-substrate transketolase reaction compared to the two-substrate reaction is due to the stage of transferring the first glycolaldehyde molecule from the thiazole ring to the aminopyrimidine ring of thiamine diphosphate. Fragmentation of the four-carbon thiamine diphosphate derivatives showed that two glycolaldehyde molecules are bound to both coenzyme rings and the erythrulose molecule is bound to a thiazole ring. It was concluded that in the one-substrate reaction erythrulose is formed on the thiazole ring of thiamine diphosphate from two glycol aldehyde molecules linked to both thiamine diphosphate rings. The kinetic characteristics were determined for the two substrates, fructose 6-phosphate and glycolaldehyde.


Assuntos
Transcetolase/química , Transcetolase/metabolismo , Acetaldeído/análogos & derivados , Acetaldeído/química , Acetaldeído/metabolismo , Biocatálise , Boroidretos/química , Coenzimas/metabolismo , Frutosefosfatos/química , Frutosefosfatos/metabolismo , Cinética , Saccharomyces cerevisiae/enzimologia , Proteínas de Saccharomyces cerevisiae/química , Proteínas de Saccharomyces cerevisiae/metabolismo , Espectrometria de Massas por Ionização por Electrospray , Especificidade por Substrato , Tetroses/metabolismo , Tiamina Pirofosfato/química , Tiamina Pirofosfato/metabolismo
12.
Methods Mol Biol ; 2346: 183-190, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-32803539

RESUMO

Cytonemes are specialized signalling filopodia that have a role in development and cellular differentiation. However, they are not well preserved by standard fixation techniques to study protein localization and interactions. A recent methodological advance has yielded improvements in cytoneme preservation using glutaraldehyde fixation and sodium borohydride treatment to reduce background. We herein describe a safer method for effective blocking using glycine following glutaraldehyde fixation of cytonemes on cultured adherent cells and demonstrate its effectiveness in immunocytochemistry.


Assuntos
Comunicação Celular , Imuno-Histoquímica , Pseudópodes/metabolismo , Boroidretos/química , Adesão Celular , Células Cultivadas , Glutaral/química , Humanos
13.
Molecules ; 25(23)2020 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-33260384

RESUMO

The cationic Pt complex (Pt(NC6H4-C6H4N-(CH2)10-O(C6H3-3,5-(OMe)2)(MeN-(CH2CH2NMe2)2))+ was prepared by the reaction of alkylbipyridinium ligand with a nitrateplatinum(II) complex. Mixing the complex and α- and ß-cyclodextrins in aqueous media produced the corresponding [2]rotaxanes with 1:1 stoichiometry. γ-Cyclodextrin and the Pt complex formed a rotaxane having components in a 1:1 or 2:1 molar ratio. The results of mass and nuclear magnetic resonance (NMR) measurements confirmed the rotaxane structures of the Pt complexes. Transmission electron microscopy (TEM) and atomic force microscope (AFM) analyses revealed the formation of micelles or vesicles. The addition of NaBH4 to the rotaxanes in aqueous media formed Pt nanoparticles with diameters of 1.3-2.8 nm, as characterized by TEM. The aggregated size of the nanoparticles formed from the rotaxane did not change even at 70 °C, and they showed higher thermal stability than those obtained from the reduction of the cyclodextrin-free Pt complex.


Assuntos
Ciclodextrinas/química , Nanopartículas Metálicas/química , Compostos Organoplatínicos/química , Platina/química , Rotaxanos/química , Boroidretos/química , Ligantes , Micelas , Microscopia de Força Atômica , Microscopia Eletrônica de Transmissão , Conformação Molecular , Compostos Organoplatínicos/síntese química , Tamanho da Partícula , Espectroscopia de Prótons por Ressonância Magnética , Soluções , Espectrofotometria , Temperatura
14.
Inorg Chem ; 59(20): 14944-14953, 2020 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-33001639

RESUMO

Application of organometallic ruthenium(II) arene complexes has been successful for the modulation of cellular redox processes via their interaction with species such as formate to control the NAD+/NADH balance in cells. Here we present the first evidence that similar effects can be reached with the application of a nonorganometallic ruthenium(II) polypyridyl complex. Kinetic studies performed demonstrate the ability of [RuII(terpy)(en)(H2O/EtOH)]2+ in water/ethanol (1:9, v/v) solution, where terpy = 2,2':6',2″-terpyridine and en = ethylenediamine, to catalyze the reduction of the NAD+ coenzyme to NADH in the presence of formate as hydride transfer source. In this case, terpy instead of arene is responsible for the labilization of coordinated solvent. The suggested catalytic cycle begins with the fast anation of the [RuII(terpy)(en)(H2O/EtOH)]2+ complex by formate. This is followed by the rate-determining formate-catalyzed decarboxylation of the generated ruthenium(II) formato complex to form [RuII(terpy)(en)H]+. Rapid hydride transfer to NAD+ from [RuII(terpy)(en)H]+ to form NADH and to regenerate the starting ruthenium(II) solvato complex, closes the overall catalytic cycle.


Assuntos
Complexos de Coordenação/química , Formiatos/química , Hidrogênio/química , NAD/química , Piridinas/química , Boroidretos/química , Catálise , Cinética , Modelos Químicos , Oxirredução , Rutênio/química
15.
Int J Biol Macromol ; 163: 1591-1598, 2020 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-32791282

RESUMO

Chitosan (CH) was N-alkylated via Schiff base formation and further reduced via sodium borohydride. The reaction was carried out at room temperature, in a homogeneous aqueous medium, using as a source of alkyl group an essential oil (Eucalyptus staigeriana) containing an unsaturated aldehyde (3,7-dimethylocta-2,6-dienal). Derivatives were characterized by Infrared Spectroscopy, proton and carbon Nuclear Magnetic Resonance, XRD, particle size distribution and zeta potential. Chitosan hydrophobization evidence was given by FTIR as new bands at 2929 cm-1 due to methyl groups, along with the presence of strong band at 1580 cm-1 owing to N substitution. Moreover, carbon and proton NMR corroborated the insertion of methyl groups in chitosan backbone. The degree of substitution was found to be in the range 0.69-1.44. X-ray diffractograms revealed that the insertion of alkyl substituents in chitosan backbone led to a less crystalline material. Data from antibacterial activity revealed that chitosan and derivatives were effective against Gram-positive bacteria, whereby derivatives exhibited greater inhibitory effect than CH. Derivatives are likely candidates for use as carriers for active principles of interest of food, pharmacy and medicine.


Assuntos
Quitosana/química , Alquilação , Antibacterianos/química , Antibacterianos/farmacologia , Boroidretos/química , Bactérias Gram-Positivas/efeitos dos fármacos , Espectroscopia de Ressonância Magnética/métodos , Testes de Sensibilidade Microbiana/métodos , Óleos Voláteis/química , Bases de Schiff/química , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Difração de Raios X/métodos
16.
Carbohydr Polym ; 245: 116543, 2020 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-32718638

RESUMO

Cationic hydrogels with amino groups were successfully prepared using (1→3)-α-d-glucan synthesized by glucosyltransferase J (GtfJ) cloned from Streptococcus salivarius through a three-step reaction: (i) Azido groups were regioselectively introduced at the C6 position of (1→3)-α-d-glucan by a bromination-azidation process (degree of substitution 0.94), (ii) Azido groups were partially crosslinked with 1,8-nonadiyne via a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, (iii) Azido groups that were unused for crosslinking were reduced to amino groups by sodium borohydride (NaBH4). The introduction of amino groups was confirmed quantitatively and qualitatively by elemental, Fourier transform infrared (FT-IR), and nuclear magnetic resonance (NMR) analyses. These cationic hydrogels showed a specific adsorption ability for bovine serum albumin (BSA) over a wide pH range of 4.5-8.0 due to their high pH values at the point of zero charge (pHpzc 8.80-8.92).


Assuntos
Azidas/química , Cátions/química , Reagentes de Ligações Cruzadas/química , Glucanos/química , Hidrogéis/química , Adsorção , Alcinos/química , Aminação , Boroidretos/química , Cobre/química , Reação de Cicloadição , Glucanos/síntese química , Glucosiltransferases/química , Glucosiltransferases/genética , Concentração de Íons de Hidrogênio , Espectroscopia de Ressonância Magnética , Organismos Geneticamente Modificados , Soroalbumina Bovina/química , Espectroscopia de Infravermelho com Transformada de Fourier , Streptococcus salivarius/enzimologia , Streptococcus salivarius/genética , Sacarose/química
17.
ChemMedChem ; 15(18): 1741-1751, 2020 09 16.
Artigo em Inglês | MEDLINE | ID: mdl-32667720

RESUMO

An alternative method to prepare 2-organylchalcogenopheno[2,3-b]pyridines was developed by the insertion of chalcogen species (selenium, sulfur or tellurium), generated in situ, into 2-chloro-3-(organylethynyl)pyridines by using the NaBH4 /PEG-400 reducing system, followed by an intramolecular cyclization. It was possible to obtain a series of compounds with up to 93 % yield in short reaction times. Among the synthesized products, 2-organyltelluropheno[2,3-b]pyridines have not been described in the literature so far. Moreover, the compounds 2-phenylthieno[2,3-b]pyridine (3 b) and 2-phenyltelluropheno[2,3-b]pyridine (3 c) exhibited significant antioxidant potential in different in vitro assays. Further studies demonstrated that compound 3 b exerted an antinociceptive effect in acute inflammatory and non-inflammatory pain models, thus indicating the involvement of the central and peripheral nervous systems on its pharmacological action. More specifically, our results suggest that the intrinsic antioxidant property of compound 3 b might contribute to attenuating the nociception and inflammatory process on local injury induced by complete Freund's adjuvant (CFA).


Assuntos
Analgésicos/farmacologia , Antioxidantes/farmacologia , Boroidretos/química , Calcogênios/química , Inflamação/tratamento farmacológico , Dor/tratamento farmacológico , Polietilenoglicóis/química , Analgésicos/síntese química , Analgésicos/química , Animais , Antioxidantes/síntese química , Antioxidantes/química , Modelos Animais de Doenças , Relação Dose-Resposta a Droga , Adjuvante de Freund/efeitos adversos , Inflamação/induzido quimicamente , Masculino , Camundongos , Estrutura Molecular , Oxirredução , Dor/induzido quimicamente
18.
Molecules ; 25(9)2020 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-32397552

RESUMO

Ruthenocene-based PCPtBu pincer ligands were used to synthesize novel pincer palladium chloride RcF[PCPtBu]PdCl (2a) and two novel palladium tetrahydroborates RcF[PCPtBu]Pd(BH4) (3a) and Rc*[PCPtBu]Pd(BH4) (3b), where RcF[PCPtBu] = κ3-{2,5-(tBu2PCH2)2-C5H2}Ru(CpF) (CpF = C5Me4CF3), and Rc*[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp*) (Cp* = C5Me5). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in 3a and 3b relative to non-substituted Rc[PCPtBu]Pd(BH4) analogue (3c; where Rc[PCPtBu] = κ3-{2,5-(tBu2PCH2)2C5H2}Ru(Cp), Cp = C5H5) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom. This displacement increases in the order 3c < 3b < 3a following the order of the Cp-ring steric volume increase. The analysis of both X-ray and IR data suggests that BH4 ligand in both palladium tetrahydroborates 3a and 3b has the mixed coordination mode η1,2. The strength of the BH4 bond with palladium atom increases in the order Rc[PCPtBu]Pd(BH4) < Rc*[PCPtBu]Pd(BH4) < RcF[PCPtBu]Pd(BH4) that appears to be affected by both steric and electronic properties of the ruthenocene moiety.


Assuntos
Boroidretos/química , Compostos Organometálicos/química , Paládio/química , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Espectroscopia de Infravermelho com Transformada de Fourier
19.
Appl Biochem Biotechnol ; 192(1): 243-256, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32372381

RESUMO

The biorefinery concept makes use of renewable lignocellulosic biomass to produce commodities sustainably. A synthetic microbial consortium can enable the simultaneous utilization of sugars such as glucose and xylose to produce biochemicals, where each consortium member converts one sugar into the target product. In this study, woody biomass was used to generate glucose and xylose after pretreatment with 20% (w/v) sulfuric acid and 60-min reaction time. We compared several strategies for detoxification with charcoal and sodium borohydride treatments to improve the fermentability of this hydrolysate in a defined medium for the production of the growth-associated product pyruvate. In shake flask culture, the highest pyruvate yield on xylose of 0.8 g/g was found using pH 6 charcoal-treated hydrolysate. In bioreactor studies, a consortium of two engineered E. coli strains converted the mixture of glucose and xylose in batch studies to 12.8 ± 2.7 g/L pyruvate in 13 h. These results demonstrate that lignocellulosic biomass as the sole carbon source can be used to produce growth-related products after employing suitable detoxification strategies.


Assuntos
Escherichia coli/metabolismo , Lignina/química , Engenharia Metabólica , Piruvatos/metabolismo , Madeira , Biomassa , Reatores Biológicos , Boroidretos/química , Fermentação , Glucose/química , Concentração de Íons de Hidrogênio , Hidrólise , Consórcios Microbianos , Microrganismos Geneticamente Modificados , Ácido Pirúvico/química , Saccharomyces cerevisiae/metabolismo , Ácidos Sulfúricos/química , Temperatura , Xilose/química
20.
Anal Chim Acta ; 1111: 8-15, 2020 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-32312400

RESUMO

Recently, the use of atomic spectrometry (AS) for biochemical analysis has attracted considerable attention due to its high sensitivity, selectivity and anti-interference ability. In this work, we conducted a detailed study on a phenomenon of thiol inhibition of mercury (Hg2+) cold vapor generation (CVG) and found L-cysteine (L-Cys), glutathione (GSH), dithiothreitol, N-Acetyl-L-cysteine, 3-mercaptopropionic acid, ß-mercaptoethanol, and NaI can inhibit the CVG of Hg2+, while EDTA has no inhibitory effect. Furthermore, changing the content of -SH can effectively adjust the CVG atomic fluorescence spectrometer (CVG-AFS) signal of Hg2+. As as a consequence, an AS-based homogeneous bioassay was constructed by adjusting the oxidation ratio and production quantity of -SH in the system. The quantitative analysis of the system was demonstrated by using AFS as a representative detector. Hydrogen peroxide (H2O2) and glucose were used as representative analytes for the validation of Hg2+ atomic fluorescence signal turn-off strategy, and butyrylcholinesterase (BChE) as well as parathion (organophosphorus pesticides, OPs) as utilized as representative targets for the signal turn-on strategy. Under optimal experimental conditions, the homogeneous CVG-AFS sensor can be successfully used to detect 3 µM H2O2, 30 µM glucose, 0.25 U/L BChE, and 0.4 µg/mL parathion. In addition, the detection results of glucose and BChE in human serum samples agreed well with those obtained by using glucometer and kit, showing the promising potential of this method for practical applications. Therefore, this work provides a perspective for the construction of AS-based homogeneous bioassays and shows great potential for the detection of biomarkers.


Assuntos
Butirilcolinesterase/análise , Glucose/análise , Peróxido de Hidrogênio/análise , Praguicidas/análise , Bioensaio , Boroidretos/química , Butirilcolinesterase/metabolismo , Humanos , Mercúrio/química , Espectrofotometria Atômica , Compostos de Sulfidrila/química , Compostos de Estanho/química , Volatilização
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